Simultaneous speciation analysis of Hg and Se in fish by high-performance liquid chromatography and inductively coupled plasma-mass spectrometry following microwave-assisted enzymatic hydrolysis.

This study reports the development and validation of a new analytical method for simultaneous speciation analysis of Se and Hg in fish muscle. For this purpose, four Se species (selenite/Se(IV), selenate/Se(VI), selenomethionine/SeMet, and selenocysteine/SeCys) and two Hg species (inorganic mercury/iHg and methylmercury/MeHg) were extracted simultaneously by microwave-assisted enzymatic hydrolysis and then separated by HPLC in less than 15 min by using a column with both anion and cation exchange mechanisms and a mobile phase consisting of a mixture of methanol 5% (v/v), 45 mM HNO3, 0.015% 2-mercaptoethanol, and 1.5 mM sodium 3-mercapto-1-propanesulfonate. The separated species of Hg and Se were detected online by inductively coupled plasma-mass spectrometry (ICP-MS). The speciation analysis method was validated by means of the accuracy profile approach by carrying out three series of measurements in duplicate on three different days over a time-span of 3 weeks. The limits of quantification (LOQ) are in the range of 0.010-0.013 mg/kg wet weight (ww) for all selenium species, except for Se(IV) (0.15 mg/kg ww), while the coefficient of variation in terms of intermediate reproducibility (CVR) was < 7%. The LOQ for MeHg was 0.006 mg/kg ww, while the CVR was 3%. The method was successfully applied to the analysis of muscle samples from four different fish species: rainbow trout, tuna, swordfish, and dogfish.

Assessment of the mercury-selenium antagonism in rainbow trout fish.

This study aims at the assessment of mercury (Hg)-selenium (Se) antagonism in fish. For this purpose, rainbow trout fish (Oncorhynchus mykiss) were exposed to methylmercury (MeHg) under controlled conditions, in the presence or absence of selenomethionine (SeMet) using an in-house prepared diet (enriched with MeHg and SeMet at 0.2 µg/g and 5.0 µg/g, respectively). The total duration of the exposure study was 3 months. Fish was sampled and analysed for total Se (SeT) and total mercury (HgT) content after 1, 2 and 3 months of exposure. Six feeding protocols were compared, depending on the exposure type: (i) no MeHg nor SeMet exposure (control group); (ii) exposure to SeMet solely; (iii) exposure to MeHg solely; (iv) exposure to both MeHg and SeMet; (v) exposure first to MeHg during 1 month and then to SeMet during 2 months and (vi), exposure to SeMet during 1 month and then to MeHg for 2 months. The levels of SeT and HgT in the fish (control and supplemented with MeHg/SeMet) were measured by inductively coupled plasma-mass spectrometry (ICPMS). Steadily (linear) bioaccumulation of MeHg in the fish muscle occurred when the fish were exposed individually to this species during the period. The bioaccumulation of MeHg is diminished when the fish are firstly exposed to SeMet and then to MeHg, hence indicating the MeHg detoxification due to SeMet supplementation.

Trace element contamination in fish impacted by bauxite red mud disposal in the Cassidaigne canyon (NW French Mediterranean).

From 1966 to 2015, the Gardanne alumina refinery discharged some 20 million tons of bauxite residue (called red mud) into the Cassidaigne Canyon (northwest French Mediterranean) with impacts on local ecosystem functioning. Although these red muds contained high levels of trace elements (TE), in particular titanium (Ti), vanadium (V), aluminum (Al) and arsenic (As), surprisingly, their impacts on fish contamination levels and the risk related to fish consumption have been little studied until now. Here, 11 trace elements (Al, As, Cd, Cr, Co, Cr, Mn, Ni, Pb, Ti and V) were analyzed in muscle and, when possible, liver, from 1308 fish of 26 species from an impacted zone in the vicinity of the Cassidaigne Canyon and a reference zone, unaffected by red mud disposals. Moreover, 66 arsenic speciation analyses were performed. Although the impact of human activities on the levels of fish contamination by trace elements is generally not easy to assess in situ because it is blurred by interaction with biological effects, we highlighted significant contamination of the fish species collected from the Cassidaigne Canyon, especially by the main trace elements attributable to the discharges of the Gardanne alumina refinery, namely Al, V and Ti. Moreover, inorganic toxic As concentrations were higher in the impacted zone. The results of this baseline research also confirmed the concern previously raised regarding Hg in Mediterranean organisms and that trace element contamination levels in fish are generally negatively related to fish length for all TE except Hg.